Two Carboxyl-Decorated Anionic Metal-Organic Frameworks as Solid-State Electrolytes Exhibiting High Li+ and Zn2+ Conductivity

Xing Duan; Yuan Ouyang; Qinghan Zeng; Shiyu Ma; Zhe Kong; Aqing Chen; Zhiwei He; Tao Yang; Qi Zhang

doi:10.1021/acs.inorgchem.1c00744

Two Carboxyl-Decorated Anionic Metal-Organic Frameworks as Solid-State Electrolytes Exhibiting High Li⁺ and Zn²⁺ Conductivity

Inorg Chem. 2021 Aug 2;60(15):11032-11037. doi: 10.1021/acs.inorgchem.1c00744. Epub 2021 Jul 11.

Authors

Xing Duan^{1

2}, Yuan Ouyang³, Qinghan Zeng³, Shiyu Ma¹, Zhe Kong¹, Aqing Chen¹, Zhiwei He¹, Tao Yang¹, Qi Zhang³

Affiliations

¹ Center of Advanced Optoelectronic Materials and Devices, Key Laboratory of Novel Materials for Sensor of Zhejiang Province, College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China.
² State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China.
³ Guangzhou Key Laboratory of Low-Dimensional Materials and Energy Storage Devices, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China.

PMID: 34250806
DOI: 10.1021/acs.inorgchem.1c00744

Abstract

A highly electronegative carboxyl-decorated anionic metal-organic framework (MOF), (Me₂NH₂)₂[In₂(THBA)₂](CH₃CN)₉(H₂O)₂₁ (InOF; H₄THBA = [1,1':4',1″-terphenyl]-2',3,3″,5,5',5″-hexacarboxylic acid), with high-density electronegative functional sites was designed and constructed. One unit cell of InOF possesses 12 negative sites that originate from the negatively charged secondary building unit [In(COO)₄]^- and exposed carboxyl groups on the ligand. The abundant electronegative sites can facilitate the hopping of ions in channels and thus result in highly efficient ion conductivities for various metal ions. Our results show that Li⁺-loaded materials have a remarkably high ion conductivity of 1.49 × 10^-3 S/cm, an ion transference number of 0.78, and a relatively low activation energy of 0.19 eV. The Na⁺, K⁺, and Zn²⁺ ion conductivities of InOF are 7.97 × 10^-4, 7.69 × 10^-4, and 1.22 × 10^-3 S/cm at 25 °C, respectively.